JPH11160501A - Photochromic plastic lens and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photochromic plastic lens having high durability and high photochromic performance at a low cost with high productivity by treating the surface of a plastic lens base body to give permeability and depositing a photochromic material thereon to permeate. SOLUTION: The surface of a plastic lens base body is treated to give permeability. A photochromic material is deposited on the base body after the treatment to allow the photochromic material to permeate. The surface where the photochromic material is to be deposited is made porous to improve the permeability for the photochromic material. The surface where the photochromic material is to be deposited means the surface of a plastic lens base body or surfaces of a primer layer or a hard coating layer formed on the base body. As for the depositing method of the photochromic material, vapor deposition or vacuum vapor deposition is preferably used. Otherwise, a dry process such as sputtering and CVD can be used.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a photochromic plastic lens and a method for manufacturing the same.

[0002]

2. Description of the Related Art In recent years, plastic lenses have been widely used as optical lenses, especially for spectacles, because of their characteristics such as being easy to mold, light and hard to break, and being easily colored by dyeing. Have been. Recently, studies have been made on spectacle lenses having photochromic performance. However, conventional lenses using plastic lenses are more problematic in terms of functions related to photochromic performance such as coloring density, coloring speed, fading speed, and durability of dimming performance than those using inorganic glass lenses. It was inferior.

Conventionally, the following method has been considered as a method for imparting photochromic performance to a plastic lens. 1. 1. A method in which a photochromic compound (hereinafter referred to as a photochromic substance) is mixed with a powder or a granular material to be a plastic lens substrate and then melt-kneaded. 2. A method in which a photochromic substance is dispersed and dissolved in a monomer of a liquid plastic material to be a plastic lens substrate and then polymerized. 3. A method of dispersing a photochromic substance in an appropriate solvent and then impregnating the cured plastic lens substrate. 4. A method in which a photochromic substance is dispersed in an appropriate solvent, applied to a plastic lens substrate, and then heated to allow the photochromic substance to penetrate the plastic lens substrate. A method of dispersing and dissolving a photochromic substance in a solution containing an appropriate polymer and / or monomer and, if necessary, a solvent, coating the surface of various substrates such as inorganic glass and plastic, and drying and / or curing. It is.

[0004]

However, the above-mentioned conventional methods 1 and 2 are not suitable for producing plastic lenses for correcting eyesight. The reason is as follows. The photochromic plastic lenses formed by the methods 1 and 2 are cured in a state where the photochromic substance is uniformly dispersed in the lenses. Generally, in a spectacle lens, since the thicknesses of the central portion and the outer peripheral portion are different, a density gradient always occurs in proportion to the thickness of the base material, and a lens having a uniform density cannot be obtained.

In the methods 3 and 4, a solvent or a solvent for dispersing the photochromic substance is used. However, there is a restriction that a solvent or a solvent of a type that does not affect the surface of the plastic lens substrate must be selected. Further, in the above method 5, types of polymers, monomers, and photochromic substances that can be coated on the surface of the plastic lens substrate are limited. In addition, a coating liquid must be prepared in advance for each color to be colored, and there is a disadvantage that productivity is extremely deteriorated.

[0006] Further, in the above-mentioned method 5, the types of the photochromic substance and the solvent are limited, and there is a disadvantage that the plastic lens substrate must not be damaged.

In the production of a dyed lens other than a photochromic plastic lens, a lens substrate is heated, a sublimable dye is heated and evaporated on a heated lens surface by resistance heating, and the sublimable dye is blown in a vacuum to heat a heated lens. Methods of attaching and penetrating to the surface are known. However, in such a method for producing a dyed lens, there is a problem that the probability of adhesion of the dye is low, and most of the dye adheres to the peripheral portion in the bell jar. Furthermore, in this method, a sublimable dye is adhered to the surface of the plastic lens substrate in a vacuum,
And it takes a considerable time as a process to penetrate the inside of the substrate by heating the substrate in vacuum,
In addition, there is a disadvantage that it is not suitable for producing a colored lens having a high density.

In the conventional method of manufacturing a photochromic plastic lens, only a photochromic lens in which the entire surface of the lens substrate discolors and discolors can be obtained. Furthermore, it has been difficult to obtain a photochromic plastic lens of two or more colors, especially three or more colors by the conventional manufacturing method.

Further, photochromic plastic lenses are often used outdoors due to their performance, and lenses must be manufactured that can withstand various environments. In particular, when a permeation region of the photochromic substance exists inside the surface of the plastic lens substrate, it is necessary to further improve durability such as scratch resistance, impact resistance, adhesion, and stain resistance.
Further, it is necessary to improve the photochromic performance such as the light control speed, which is a characteristic of the photochromic plastic lens. Furthermore, photochromic plastic lenses having these various properties must be easily and inexpensively manufactured.

Accordingly, an object of the present invention is to solve the above-mentioned problems and to manufacture a photochromic plastic lens having high durability and high photochromic performance at low cost and high productivity.

[0011]

According to the present invention, in order to solve the above-mentioned problems, the surface on which a photochromic substance is adhered is made porous (roughened) so that the photochromic substance can be more easily penetrated.

Therefore, the present invention firstly provides a “process of imparting permeability to the surface of a plastic lens substrate, a process of attaching a photochromic substance to the substrate after the treatment by a dry process, A method for producing a photochromic plastic lens (Claim 1). Second, "a step of forming a resin film on the surface of the plastic lens substrate, a step of performing a permeability imparting treatment on the surface of the resin film, and attaching a photochromic substance to the resin film after the treatment by a dry process. And a step of permeating the photochromic substance into the resin film. Third, a photochromic plastic lens characterized in that a photochromic substance is present in the vicinity of the surface of a plastic substrate subjected to a permeability imparting treatment or in the vicinity of the surface of a resin film formed on the plastic substrate. "I will provide a.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The photochromic substances according to the present invention include chromene-based, spirooxazine-based, spironaphthoxazine-based, spiropyran-based, naphthopyran-based, fulgide-based, fulgimide-based, and viologen generally used for photochromic plastic lenses. System, triarylmethane system, diarylethene system, and diazo system.

For example, a photochromic substance that can be used in the present invention has a coloring mechanism represented by the following formula:

Embedded image Spiropyran-based and spirooxazine-based substances represented by Actual photochromic substances include derivatives into which various substituents are introduced, and derivatives having slightly different skeleton structures.

For example, the following formula exemplifies various spirooxazine derivatives.

Embedded image

Also, the following equation

Embedded image

[0017]

Embedded image Flugimide-based substances and chromene-based substances represented by

## EQU1 ##

Embedded image Various derivatives of the naphthopyran series represented by are also exemplified as the photochromic substance that can be used in the present invention.

In the present invention, the surface to which the photochromic substance is adhered is made porous to improve the permeability of the photochromic substance. However, the surface to be adhered may be a primer layer or a hard coat layer formed on the surface of the plastic lens substrate or the substrate. Surface.

Further, by forming a coating of a resin on which the photochromic substance easily penetrates on the surface of the base material and making this surface porous, the permeability of the photochromic substance can be further improved.

As a method for attaching the photochromic substance, an evaporation method or a vacuum evaporation method is preferably used, but is not limited thereto. For example, sputtering method, C
A conventionally known dry process such as a VD method, an ion plating method, or a sublimation method can be used.

The vacuum deposition of the photochromic material is usually performed by heating the heater with the photochromic material placed in a crucible at a vacuum evacuation degree of 5 × 10 ⁻⁵ Torr or less. In the present invention, the heating temperature of the photochromic substance is 100 to 200 ° C. As the vacuum deposition method, a conventionally well-known method or an appropriate method related to its improvement can be adopted. For example, the photochromic substance is resistance-heated in a vacuum, and the photochromic substance scattered toward the surface of the plastic lens substrate located thereon is attached. Then, the plastic lens substrate to which the photochromic substance is attached is subjected to a heat treatment.
As a result, the photochromic substance permeates the surface of the plastic lens substrate, and a plastic lens having desired photochromic performance is manufactured.

The heat treatment of the plastic lens substrate having the photochromic substance adhered to the surface may be performed in the atmosphere or in an inert gas atmosphere under atmospheric pressure, which is another important feature of the present invention. is there. Of course, if desired, reduced pressure conditions may be employed.

The heating may be performed together with the vacuum deposition of the photochromic substance on the surface of the plastic lens substrate, but a method in which the heating is not performed at the same time is preferable. By heating the substrate at the time of vapor deposition, it is possible to perform the penetration together with the adhesion to the substrate or the surface of the resin film, and the process can be shortened. However, the vapor deposition material tends to adhere to a lower temperature region, and if the substrate is heated to a high temperature, the deposition efficiency of the vapor deposition material may be reduced, and the process may take a long time, so the efficiency is increased. In the case where the substrate is manufactured in a specific manner, a method in which the substrate is not heated is preferred. In addition, when the base material is heated, the deposition material does not adhere much to the base material in the high-temperature portion, and the ratio of the deposition material to the low-temperature portion around the base material (for example, inside the deposition apparatus) increases. is there.

The heating of the plastic lens substrate to which the photochromic substance adheres after the deposition is performed at about 100 to 200 ° C. for about 0.5 to several hours. For heating, an oven, infrared rays, electromagnetic waves, or a heat medium such as hot air, water, or oil can be used as appropriate. For example, when an oven is used, heating for a long time has a problem of heat resistance of the plastic substrate, and thus it is preferable to perform the heat treatment at a heating temperature in a relatively low temperature region for a relatively long time. In the case of infrared heating, since the heating is performed only in the vicinity of the surface of the base material, the photochromic substance can be permeated in a relatively high temperature region with a short heating time. Further, when a resin film is formed on a base material and a photochromic substance is penetrated into the resin film, cracks may occur during heating due to a difference in thermal expansion coefficient between the plastic lens base material and the resin film. It is preferable to perform heating for a long time at a low heating temperature.

In consideration of the conditions for permeation of these photochromic substances, the depth of penetration of the photochromic substance can be adjusted by appropriately controlling the heating temperature and the heating time.

According to the present invention, the amount of the photochromic substance used is about one-tenth to one-twentieth as compared with the conventional method of kneading the photochromic substance into the monomer,
A considerable cost reduction becomes possible. In addition, in the kneading method, in order to mass-produce lenses of the same color, the production of photochromic lenses of one or two colors was the limit. However, since the present invention is a batch process, it is suitable for each batch. Weighing the photochromic material allows for the production of photochromic plastic lenses of various colors.

Further, in the present invention, the photochromic substance is present in an area of about 0.1 to 100 μm in the depth direction from the surface of the substrate, and the conventional method of kneading dispersed throughout the substrate is as follows. The difference in the region where the photochromic substance exists is apparent. Considering that the photochromic substance is colored in response to ultraviolet light, the photochromic substance that contributes to coloring only needs to be present in the vicinity of the base material surface on the ultraviolet incident side. Therefore, in the conventional kneading method, a large amount of useless photochromic substances that do not contribute to coloring are contained in the entire inside of the base material. In the configuration of the present invention, it is possible to obtain a sufficient coloring despite the smaller amount of the photochromic substance used compared to the conventional method.

Further, in the present invention, since no solvent is used, there is no problem of solvent selectivity or a problem in a manufacturing process associated with the treatment of the solvent, unlike the conventional method using solvent dispersion. Furthermore, since the photochromic substance is not adhered to the base material and the plastic base material is not heated, problems such as adhesion of the dye to the inner portion of the vacuum bell jar, prolongation of the process, and difficulty in adjusting the concentration are difficult. It is possible to obtain a photochromic plastic lens which can be uniformly colored with good reproducibility, low cost and high productivity.

In consideration of the photochromic performance such as the permeability of the photochromic substance and the light control speed, it is desirable to use a material having a volume that allows the photochromic substance to easily enter the inside of the lens substrate from the surface and move freely. . For this purpose, the surface of the base material may be coated with a resin film through which the photochromic substance easily penetrates, and the photochromic substance may penetrate into a region of about 0.1 to 100 μm in a depth direction from the surface.

The plastic lens substrate used in the present invention may be of various types including conventionally known ones, for example, polymethyl methacrylate and its copolymer, acrylonitrile-styrene copolymer, polycarbonate, cellulose acetate, and poly (vinyl acetate). Plastic lens molded articles made of vinyl chloride, polyethylene terephthalate, epoxy resin, unsaturated polyester resin, polyurethane resin, diethylene glycol bisallyl carbonate polymer and the like are exemplified.

It is also possible to use an ultraviolet-curing resin or a resin having both ultraviolet-curing and thermosetting properties. A cured product made of an ultraviolet curable resin has a larger photochromic performance because the intermolecular gap after curing is larger than that of a cured product made of a thermosetting resin, so that the photochromic substance easily penetrates and changes its structure more easily. become.

As the ultraviolet-curable resin used in the present invention, the following ultraviolet-curable resins polymerized by irradiation with ultraviolet light are used. However, a combination of ultraviolet curing and thermal curing may be used as described above. In this case, a polymerization initiator that initiates polymerization by ultraviolet light and a polymerization initiator that initiates polymerization by heat are added to the monomer.

The ultraviolet polymerization reaction system requires a photopolymerization radical initiator that generates radicals by irradiation with ultraviolet light, and a monomer, oligomer, or prepolymer that undergoes radical polymerization. In addition, a sensitizer, a storage stabilizer, a polymerization stabilizer, Inhibitors, polymers and coloring materials depending on the purpose may be blended. In addition, a cationic photopolymerization system is appropriately used.
The photo-radical initiator is not particularly limited, and known ones can be used. Representative examples thereof include biacetyl, acetophenone, benzophenone, Michler's ketone, benzyl, benzoin, benzoin isobutyl ether, and benzyl dimethyl ketal. , Tetramethylthiuram sulfide, azobisisobutylnitrile, 1-hydroxycyclohexylphenone, methyl ketone peroxide, acetylacetone peroxide, t-butyl peroxide, cumene hydroperoxide, α, α'-bis (t-butylperoxyisopropyl ) Benzene, t-butylperoxyisopropyl carbonate, benzoyl peroxide, di (t-
Butylperoxy) isophthalate, t-butylperoxybenzoate, 3,3 ′, 4,4′-tetra (t-
(Butylperoxycarbonyl) benzophenone and the like.

A radically polymerizable oligomer is used to efficiently cure the photoradical species, and a polymerizable monomer is appropriately added for the purpose of adjusting the viscosity. There are various types of photopolymerized oligomers, but there are unsaturated polyester / styrene type, epoxy / Lewis acid type, polyene / thiol type and acrylate. An acrylic group is frequently used as a polymerizable unit other than the unsaturated polyester. Acrylic oligomers are broadly classified into polyester acrylate, polyurethane acrylate, epoxy acrylate, polyether acrylate, oligo acrylate, alkyd acrylate, and polyol acrylate according to their basic structure. Is possible. The important ones among them are polyester, epoxy, urethane and polyol acrylates. Main photopolymerizable monomers include monofunctional: lauryl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 1,6-hexanediol monoacrylate, dicyclopentadiene acrylate, and the like. . Bifunctional: 1,3 butanediol diacrylate, 1,4 butanediol diacrylate, 1,6 hexanediol diacrylate, diethylene glycol diacrylate, tripropylene glycol diacrylate, neopentyl glycol diacrylate, polyethylene glycol 400 diacrylate ,
Hydroxypivalic acid ester neopentyl glycol diacrylate; Furthermore, trifunctional or more: trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol hexaacrylate.

In the present invention, since the amount of the photochromic material penetrating into the base material can be controlled and the penetration depth can be easily controlled, the color density can be variously changed by gradually changing the penetration depth. Can be changed.

According to the present invention, the photochromic substance is heated, for example, after the photochromic substance is attached to the lens substrate surface, and the photochromic substance is penetrated into the substrate surface. It is possible to easily control the amount of permeation. For example, in a heating step of the lens substrate after the photochromic substance is uniformly adhered to the entire surface of the lens substrate by a vacuum evaporation method, when the photochromic substance is penetrated into the surface of the substrate by heating, the surface of the lens substrate Thermal gradient,
That is, by controlling the amount of heating of the lens substrate surface, the photochromic substance can be penetrated in a gradation form.

Further, by controlling the heating time, the amount of permeation of the photochromic substance can be controlled, so that the photochromic substance can permeate in a gradation. In other words, the photochromic material permeates relatively more in the region where the heating time is long, and the photochromic material permeates relatively little in the region where the heating time is small, so that the photochromic material can be permeated in a gradation.

As a heating source, infrared rays, electromagnetic waves, hot air,
A heating medium such as heating water or heating oil is used, but is not limited thereto.

It is also possible to manufacture a gradation-like photochromic plastic lens by controlling the amount of the photochromic substance attached. As a method of controlling the amount of adhesion, a lens substrate is installed in the upper part of the chamber of the vacuum evaporation apparatus, a shielding plate is installed near the lower part of the lens, or an upper part near the evaporation source, and a driving mechanism such as a motor is used. Move slowly. Thus, the amount of the photochromic substance adhered to the lens substrate surface is controlled, and the photochromic substance adheres in a gradation. By heating this plastic lens substrate, the photochromic substance penetrates into the lens substrate surface.However, since the plastic lens substrate to be heated has a gradient in the amount of photochromic substance attached, In addition, a gradient occurs in the amount of permeation into the substrate surface in proportion to the amount of the photochromic substance attached.
As described above, according to the present invention, a photochromic plastic lens having a concentration gradient can be easily obtained.

As the resin film formed on the surface of the base material and through which the photochromic substance can penetrate, a thermoplastic resin, a thermosetting resin, a UV-curable resin, or the like is preferable. Specific examples of the material include resins such as polyamide resin, phenol resin, butyral resin, melamine resin, polyvinyl alcohol, cellulose resin, alkyd, acryl, epoxy resin, urethane resin, polyester resin, and silicone resin. These resins can be used alone or as a mixture or copolymer of several types. These resins function as a primer layer for improving impact resistance and adhesion. The resin film can be adjusted by the amount of the photochromic substance to be permeated. When the photochromic substance is allowed to penetrate into a resin film which is easily penetrated, for example, the photochromic substance penetrates the entire resin film. Therefore, when it is desired to allow a large amount of the photochromic substance to penetrate, it is possible to obtain a photochromic lens having a high concentration by increasing the thickness of the resin film. In addition, if the heating time and the heating temperature are controlled, the photochromic substance does not have to permeate the entire resin film.

When the resin film is a film having a special function such as a primer layer and a hard coat layer, it is necessary to have a film thickness that achieves the function. For example, when a resin film is used as the primer layer, the thickness is preferably about 0.5 to several μm in consideration of impact resistance and cracks.

When formed on the surface of a plastic lens substrate, it is preferable to appropriately select the combination of the type of photochromic substance to be used and the substrate material, and the film thickness.

In order to improve the scratch resistance, it is effective to form a hard coat layer, and the surface of the hard coat layer can be made porous. As the hard coat layer, a liquid polymer (hard coat liquid) containing an organic silicon compound as a main component can be used. Especially,
An organosilicon compound represented by the following general formula or a hydrolyzate thereof is preferred.

General formula: R¹aR^TwobSi (OR^Three) _{4- (a + b)} (However, in the formula, R¹Has a functional group or an unsaturated double bond.
Having 4 to 14 carbon atoms,^TwoHas 1 to 1 carbon atoms
6 is a hydrocarbon group or a halogenated hydrocarbon group,^Three
Represents an alkyl group having 1 to 4 carbon atoms, an alkoxyalkyl group or
Is an acyl group, and a and b are each 0 or 1.
And a + b is 1 or 2. )

Among the compounds of the above general formula, those in which R ¹ has an epoxy group as a functional group include, for example, the following compounds.

Since these have an epoxy group, they are also called epoxysilanes. Specific examples of the epoxy silane include, for example, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane,
γ-glycidoxypropyltrimethoxyethoxysilane, γ-glycidoxypropyltriacetoxysilane,
γ-glycidoxypropylmethyldimethoxysilane, γ
-Glycidoxypropylmethyldiethoxysilane, β-
(3,4-epoxycyclohexyl) ethyltriethoxysilane and the like.

Examples of compounds of the above general formula other than those in which R ¹ has an epoxy group as a functional group (including those in which a = 0) include the following.
Methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinyltrimethoxyethoxysilane, γ-methacryloxypropyltrimethoxysilane, aminomethyltrimethoxysilane, 3-
Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, phenyltrimethoxysilane,
Various trialkoxysilanes such as phenyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, trisiloxysilane or trialkoxyalkoxysilane compounds.

The above-exemplified compounds of the above general formula are as follows:
In each case, there are three OR ³ groups bonded to the Si atom (a +
b = 1) This is an example of trifunctionality, but there are two OR ³ groups (b
= 2) Bifunctional equivalents can of course also be used. Examples of bifunctional equivalent compounds include dimethyldimethoxysilane, diphenyldimethoxysilane,
Examples include methylphenyldimethoxysilane, methylvinyldimethoxysilane, dimethyldiethoxysilane, and the like.

The compounds of the above general formula may be used alone or in combination of two or more according to the purpose.

In particular, when a bifunctional compound is used, it is preferable to use it in combination with a trifunctional compound. When they are used together, 2> a + b> 1 on average.

Furthermore, it is also possible to use a compound corresponding to a tetrafunctional compound wherein a + b = 0. Examples of tetrafunctional equivalents include methyl silicate, ethyl silicate, isopropyl silicate, n-propyl silicate, n-butyl silicate, t-butyl silicate, s
ec-butyl silicate and the like.

The compound of the above general formula may be used as it is, but is preferably used as a hydrolyzate for the purpose of increasing the reaction rate and lowering the curing temperature. When two or more compounds having the same functional number are used in combination of two or four functional compounds, or two or more compounds having different functional numbers are used in combination, they may be used together after hydrolysis, Hydrolysis may be carried out together with the above. Upon hydrolysis, the alcohol HOR ³ is released, and the compound of the above general formula becomes the corresponding silanol. Silanol rapidly undergoes dehydration condensation to become an oligomer. Therefore, after hydrolysis, the reaction may be left (cured) for 1 to 24 hours so that this reaction proceeds sufficiently.

When these compositions are used, it is possible to add a sol to improve the hardness, prevent the occurrence of interference fringes, and further impart antistatic performance. In addition, various solvents such as water, lower alcohol, acetone, ether, ketone, and ester can be used in order to improve the flowability at the time of coating and improve the smoothness of the cured film.

A fine inorganic oxide can be mixed in the hard coat layer. By mixing the inorganic oxide, it is possible to adjust the refractive index and the hardness. As the sol, for example, zinc oxide, silicon oxide,
Fine particles of aluminum oxide, titanium oxide, zirconium oxide, tin oxide, beryllium oxide, antimony oxide, tungsten oxide, cerium oxide, tin oxide, and tungsten oxide can be used. In addition, these fine particles can be used not only alone but also in a mixed or composite state of two or more kinds as necessary.
For example, a modified state in which tin oxide fine particles are used as cores and coated with fine particles of a composite form of tungsten oxide and tin oxide can be used. Such a modified state does not aggregate in a solvent and forms a good dispersion state.
In particular, when titanium oxide, antimony oxide, tungsten oxide, cerium oxide, zirconium oxide, or tin oxide is used, the refractive index of the composition can be increased.

As a dispersion medium of the fine particles, water, alcohol or other organic solvent is used, and it is preferable to add an organic amine or other stabilizer.

The particle diameter of the fine particles is preferably 1 to 200 μm, particularly preferably 5 to 100 μm. If it is smaller than this, the production is difficult, the stability of the fine particles themselves is poor, and the effect is small. If it is larger than this, the stability of the coating composition, the transparency and the smoothness of the coating film, etc. will be reduced. Such sols are partially available as commercial products.

As the coating method, a usual coating method such as brush coating, dipping, roll coating, spray coating, and flow coating can be used. At this time, the application conditions are determined mainly by the properties of the vehicle.

By forming the hard coat layer on the surface of the plastic lens substrate as described above, scratch resistance and abrasion resistance can be improved, and deterioration of the photochromic substance permeating the substrate can be prevented. It is possible to obtain a highly durable photochromic lens in which the photochromic performance does not decrease for a long time. Therefore, it can be used under various use conditions.

In addition to the wet method, the hard coat layer can be formed by a dry CVD method. Also in this case, the surface of the hard coat layer can be made porous. When the hard coat layer is formed by the CVD method, it is preferable to form the hard coat layer after forming the modified layer on the substrate surface, but it is also possible to form only the hard coat layer.

The modified layer in the present invention is a layer formed on the surface of the base material and having a refractive index gradually changing from the base material side in the film thickness direction. And the composition ratio of the substance in the modified layer is gradually changing. It has also been confirmed that the impact resistance is improved by providing a modified layer. This was because the internal stress of the hard coat layer was high because the thickness of the conventional hard coat layer was 3 μm or more, but the hard coat layer was provided between the base material and the hard coat layer. This is because the internal stress remaining in the layer can be reduced. Therefore, since the internal stress can be reduced, there is also an effect that cracks caused by hot water resistance and heat resistance can be avoided.

The organic compounds containing Si used for the production of the modified layer and the hard coat layer include tetraethoxysilane, dimethoxysilane, methylmethoxysilane, tetramethoxysilane, ethyltrimethoxysilane, diethoxydimethylsilane, methyltriethoxysilane. Silane or the like is preferably used. Further, as an organic compound containing Ti,
Tetramethoxytitanium, tetraethoxytitanium, tetraisopropoxytitanium, tetra-n-propoxytitanium, tetra-n-butoxytitanium, tetraisobutoxytitanium, tetra-sec-butoxytitanium, tetra-t
-Butoxytitanium, tetradiethylaminotitanium and the like are preferably used.

These organic compounds of Si and Ti are
One type may be used alone, or two or more types may be used in combination.

The thickness of the hard coat layer is preferably larger than 0.4 μm and smaller than 5 μm. In addition, the thickness of the denatured layer is more than 100 nm and preferably less than 900 nm.

By forming the hard coat layer by CVD in this manner, a photochromic lens having high durability can be easily manufactured only by a dry method.

It is also possible to form a primer layer on the surface of the plastic lens substrate. The surface of the primer layer can be made porous as in the case of the hard coat layer. By forming the primer layer, the adhesion between the hard coat layer formed thereon and the substrate can be improved, and the impact resistance can also be improved. This makes it possible to manufacture a photochromic plastic lens that has excellent durability against impact, has higher durability, and can withstand various use environments.

Materials used for the primer layer include:
A urethane-based material can be preferably used. The composition of the primer layer comprising a urethane-based material comprises an active hydrogen-containing compound and a polyisocyanate. Furthermore,
In addition to the urethane-based material, the primer layer can be formed from a material made of polyvinyl acetal or / and cross-linked polyvinyl acetal. The polyvinyl acetal-based primer layer dissolved the polyvinyl acetal, which is the main component, and the hydrolyzable organosilane compound or its hydrolyzed condensate, an aluminum or titanium alkoxide compound or an aluminum or titanium alkoxide diketonate compound and a curing catalyst. Apply the primer composition to the plastic lens surface,
It can be formed by heat treatment.

The amount of the organosilane compound in the primer composition is 0.01 to 10% by weight, preferably 0.1 to 5% by weight.

The method of applying the primer composition on the plastic optical component in the present invention is not particularly limited as long as it is a known method such as a spin coating method and a dipping method.
In addition, it is preferable that the surface of the plastic optical component be subjected to a pretreatment such as an alkali treatment, a plasma treatment, or an ultraviolet treatment as necessary.

The thickness of the primer layer after curing is 0.1 to
It is 5 μm, preferably 0.2 to 3 μm. If the thickness of the primer layer is less than 0.1 μm, the impact resistance is not sufficiently improved, and if it is more than 5 μm, there is no problem in terms of the impact resistance, but the heat resistance and surface accuracy are reduced.

In the primer solution, it is possible to mix fine inorganic oxides mixed in the hard coat layer as described above. By mixing the fine particles, effects such as adjustment of refractive index and improvement of hardness can be provided. As these fine particles, commercially available fine particles dispersed in water or an organic solvent can be used as they are.

The average particle diameter of the finely divided inorganic oxide or the composite of these fine particles is from 1 to 300 nm, preferably from 1 to 50 nm. If the average particle diameter exceeds 300 nm, fogging of the lens occurs due to light scattering.

The addition amount of the fine particles in the primer composition is 0.1 to 30% by weight as the solid content concentration, but the refractive index of the cured primer layer matches or very close to the refractive index of the plastic lens. Thus, the type and amount of the inorganic oxide fine particles are adjusted.

In the case of a high refractive index plastic lens substrate having a refractive index of 1.60 or more, a high refractive index of titanium oxide, zirconium oxide, iron oxide, antimony oxide, oxide It is preferable to add 1 to 5 parts by weight of fine particles of tin, cerium oxide, tungsten oxide, or the like, or a composite thereof, or a mixture thereof. These inorganic fine particles can be added to a primer layer made of a urethane-based material.

The thickness of the primer layer is 0.01 to 30 μm.
m is preferred. Particularly preferably, 1 to 20 μm
It is.

The method for applying the resin for forming the primer layer is appropriately selected from known methods such as a spinner method, a dipping method and a spray method, and can be formed by a dry method such as a CVD method or a vacuum evaporation method. It is.

The primer layer can be formed on a photochromic lens having the above-mentioned gradation or a multicolored photochromic plastic lens, and has excellent fashionability and a highly durable photochromic plastic lens which can be used in various environments. Can be manufactured.

It is also possible to form a primer layer on a resin film formed on the plastic lens substrate as described above.

On the primer layer, a hard coat layer made of the above-mentioned organosilicon compound and formed by a conventional wet method or a hard coat layer formed by a CVD method can also be formed. This makes it possible to produce a photochromic plastic lens that is excellent in fashionability and more excellent in durability such as scratch resistance and impact resistance.

Further, an antireflection film may be formed. The antireflection film is preferably a single layer or a multilayer of an inorganic oxide as is generally known. By forming the antireflection film, reflection on the substrate is reduced, and photochromic performance can be made more vivid.

Further, a water-repellent film may be formed on the uppermost layer. As the water-repellent material, a material containing a fluorine group-containing organosilane compound as a main component can be preferably used. Moreover, it has an alkoxy group and / or an amino group as a functional base material,
1-3 functional ones can be used. As a forming method, an immersion method, an evaporation method, a sputtering method, or the like can be used.

By forming the water-repellent film in this way, it is possible to prevent drainage and dirt, and it is possible to maintain the vividness of the photochromic performance.

In the present invention, examples of the permeability imparting treatment for infiltrating the photochromic substance include a plasma treatment, a chemical treatment with a solution such as an acid and an alkali, a treatment by sputtering, and the like, but are not limited thereto. Instead, any method may be used as long as the surface into which the photochromic substance penetrates can be made relatively porous or hard.

For example, in the plasma processing method, a base material or a base material having a resin film formed on the base material is placed in a plasma generator. Then, for example, oxygen gas or the like is introduced into the apparatus, and after reducing the pressure, oxygen plasma is generated. The surface exposed to the generated plasma is roughened by the plasma or the resin bond is broken. Will be

[0085]

Example 1 As a plastic lens substrate, a thermosetting urethane resin plastic lens for spectacles was used.

For the hard coat layer, a silicone resin was used. The method of forming the hard coat layer is as follows. γ-glycidoxypropyltrimethoxysilane 1
80

To the part was added 40 parts by weight of a 0.01 hydrochloric acid aqueous solution, and hydrolysis was continued for 1 hour to obtain a partially condensed hydrolyzate. The above hydrolyzate is added to Nissan Chemical Co., Ltd. SnO
₂ / WO ₃ composite particles dispersed methanol sol (HIS-30
630 parts by weight of MN), 4 parts by weight of aluminum ethylenediaminetetraacetate as a curing catalyst, and a silicon-based surfactant S manufactured by Toray Dow Corning Co., Ltd. as a leveling agent.
After adding 0.45 part by weight of H30PA and sufficiently stirring and mixing, the mixture was filtered through a 3 μm membrane filter to obtain a coating composition in the form of a solution. The hard coat composition was applied to both surfaces of the plastic lens substrate by a dipping method, and heat-treated at 100 ° C. for 4 hours to cure, thereby forming a hard coat layer.

Next, plasma processing was performed as follows.
Oxygen plasma was used for the plasma treatment. The plastic lens substrate on which the hard coat layer was formed was introduced into a vacuum chamber of a plasma apparatus, and after reducing the pressure to 0.2 Torr, an oxygen gas was flowed at a flow rate of 50 SCCM, and plasma treatment was performed at a high frequency output of 150 W for 60 seconds.

Next, the deposition of a photochromic substance was performed as follows. As the photochromic substance, a chromene-based substance and a spirooxazine-based substance were used, and these substances were sufficiently mixed according to a previously determined blending ratio so as to develop a brown color. . The lens substrate was set 10 cm above the evaporation source. In addition, a quartz oscillation type film forming controller (Japan Vacuum Technology Co., Ltd .: CRTM-5000) and a vapor deposition sensor (Japan Vacuum Technology Co., Ltd .: CRTS-4)
The film thickness was controlled at 0.1 μm.

The degree of vacuum was reduced to 5 × 10 ⁻⁵ Torr by a pump, and then the evaporation source was heated to scatter the photochromic substance and adhered to the surface of the hard coat layer covering the lens substrate. The lens substrate having the photochromic substance adhered to the surface of the hard coat layer was colorless and transparent, and a slight interference color was observed.

The lens substrate was placed in a hot air oven at 120
Heating was performed at 1 ° C. for 1 hour to allow the photochromic substance adhered to the surface of the hard coat layer to permeate and diffuse inside the surface of the hard coat layer. The photochromic substance remaining on the surface without permeating into the inside of the surface of the hard coat layer was washed away with a washing machine.

Next, for abrasion resistance and antireflection, Si
An inorganic multilayer thin film composed of O ₂ , Al ₂ O ₃ , and TiO ₂ was formed by a vacuum deposition method. The photochromic plastic lens thus produced had no initial coloring and was colored brown without unevenness under sunlight.

[0093]

As described above, according to the present invention, the surface to which the photochromic substance adheres and penetrates is made porous, so that the photochromic substance can be easily penetrated. Therefore, a photochromic plastic lens can be manufactured at a lower cost than a conventional wet method such as a dipping method and a kneading method, and the manufactured lens has stable photochromic performance.

Further, since the photochromic substance is present on the surface of the hard coat layer, the ultraviolet rays for coloring the photochromic substance are efficiently absorbed, so that the amount of the photochromic substance used can be reduced, and a lower cost photochromic plastic lens can be obtained. Can be

When a film such as a resin film, a primer layer, and a hard coat layer is formed on the surface of the substrate, and the surface is made porous, the photochromic substance is adhered and penetrated.
Since the photochromic properties do not depend on the plastic lens substrate, a photochromic plastic lens with higher productivity and lower cost can be obtained. Further, a film formed with a coating such as a primer layer and a hard coat layer is excellent in appearance and has high durability, so that it can provide a photochromic plastic lens that can be adapted to spectacle wearers of various tastes under various environments. Can be.

Claims (6)

[Claims] 1. A step of applying a permeability to the surface of a plastic lens substrate, a step of attaching a photochromic substance to the substrate after the treatment by a dry process, and a step of penetrating the photochromic substance into the substrate. A method for producing a photochromic plastic lens. 2. A step of forming a resin film on the surface of a plastic lens substrate, a step of imparting permeability to the surface of the resin film, and attaching a photochromic substance to the resin film after the treatment by a dry process. And a step of infiltrating the photochromic substance into the resin film. 3. A photochromic plastic lens characterized in that a photochromic substance is present near the surface of a plastic substrate subjected to a permeability imparting treatment or near the surface of a resin film formed on the plastic substrate. 4. A step of making the surface of the plastic lens substrate porous, a step of attaching a photochromic substance to the substrate after the treatment by a dry process, and infiltrating the photochromic substance into the substrate. A method for producing a photochromic plastic lens, comprising the steps of: 5. A step of forming a resin film on the surface of a plastic lens substrate, a step of making the surface of the resin film porous, and attaching a photochromic substance to the resin film after the treatment by a dry process. And a step of infiltrating the photochromic substance into the resin film. 6. A photochromic plastic lens characterized in that a photochromic substance is present near the surface of a plastic substrate subjected to a porous treatment or near the surface of a resin film formed on the plastic substrate.